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聚乙烯醇缩丁醛的甲苯-乙醇溶液及其非溶剂诱导相分离研究

任海东 曹秀华 赵亮 唐博武 罗继业 郑华德 高粱

任海东, 曹秀华, 赵 亮, 等. 聚乙烯醇缩丁醛的甲苯-乙醇溶液及其非溶剂诱导相分离研究[J]. 功能高分子学报,2022,35(3):1-11 doi: 10.14133/j.cnki.1008-9357.20210906001
引用本文: 任海东, 曹秀华, 赵 亮, 等. 聚乙烯醇缩丁醛的甲苯-乙醇溶液及其非溶剂诱导相分离研究[J]. 功能高分子学报,2022,35(3):1-11 doi: 10.14133/j.cnki.1008-9357.20210906001
REN Donghai, CAO Xiuhua, ZHAO Liang, TANG Bowu, LUO Jiye, ZHENG Huade, GAO Liang. Toluene-Ethanol Solution of Polyvinyl Butyral and Nonsolvent-Induced Phase Separation[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20210906001
Citation: REN Donghai, CAO Xiuhua, ZHAO Liang, TANG Bowu, LUO Jiye, ZHENG Huade, GAO Liang. Toluene-Ethanol Solution of Polyvinyl Butyral and Nonsolvent-Induced Phase Separation[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20210906001

聚乙烯醇缩丁醛的甲苯-乙醇溶液及其非溶剂诱导相分离研究

doi: 10.14133/j.cnki.1008-9357.20210906001
详细信息
    作者简介:

    任海东(1976—),男,辽宁营口人,工程师,主要从事MLCC用陶瓷材料和电子浆料用玻璃粉的研究

    通讯作者:

    曹秀华,xiuhuacao@126.com;高粱,zhaolianggdut@163.com

  • 中图分类号: O631

Toluene-Ethanol Solution of Polyvinyl Butyral and Nonsolvent-Induced Phase Separation

  • 摘要: 在片式多层陶瓷电容器(MLCC)的流延工艺中,甲苯-乙醇混合物是黏合剂聚乙烯醇缩丁醛(PVB)广泛采用的溶剂体系。本文探讨了甲苯与乙醇的体积比、PVB浓度以及流延成膜的相对湿度等因素对溶液中PVB构象以及凝聚态膜片结构的影响。PVB中存在由烷侧链排列形成的玻璃区以及由链缠结而成的无定形区。乙醇是PVB的良性溶剂,通过溶胀玻璃区,使得PVB链更加舒展;甲苯可以有效降低PVB与溶液的摩擦,并通过“成核-生长”机制发生粗化聚并,导致分子间相互作用逐渐增大。较高湿度会造成膜片缺陷;混合溶剂中乙醇的体积比过高易形成缺陷;缺陷几乎不影响膜的有效模量以及热力学性能。

     

  • 图  1  PVB的分子结构及相关物性:(A)PVB粉末体系的分子结构信息; (B) DSC和TGA曲线(N2,10 °C/min); (C) XRD衍射峰:低角(7.6o)反映主链之间的距离,高角 (19.3o) 反映了侧链之间的距离;(D) 分子链示意图

    Figure  1.  The molecular structure and related properties of PVB : (A) molecular structure information of PVB powder; (B) DSC and TGA curve (N2, 10 °C/min); (C) XRD diffraction peak: The low angle (7.6o) reflects the distance between main chains and the high angle (19.3o) reflects the distance between side chains; (D)Schematic diagram of molecular chain

    图  2  PVB溶液的热力学和动力学:(A)PVB粉末体系与不同体积比的甲苯-乙醇体系的比较溶度参数(红线:PVB的溶度参数;黑线:溶液的溶度参数) ; (B)溶液黏度(η)(测试方法:同轴圆筒)(C)回旋半径(Rg)和均方末端距(h)随甲苯-乙醇体积的变化;(D)增比黏度随 c/c* 变化;(E)增比黏度随 c/c * 变化的幂律关系; (F)不同甲苯-乙醇体积比的标度值

    Figure  2.  Thermodynamics and kinetics of PVB solution: (A) Solubility parameters of PVB powder, compared with different ratios of toluene-ethanol solutions.Red line: the polarity solution parameter of the PVB;black line: non-polar solution parameter of PVB; (B) Viscosity (η) of solutions (test method : Coaxial cylinder); (C) Radius of gyration (Rg) and the mean square end distance (h) change with the volume of toluene-ethanol; (D) The specific viscosity changes with c/c*; (E) Power law relationship of the specific viscosity changing with c/c * ; (F) Scale value of different toluene-ethanol ratios

    图  3  (A)聚合物-溶剂-非溶剂的三元相图:绿色实线表示混合物的分离线,蓝色渐变色区域表示“玻璃状”区域,橙色线表示混合物分离的平衡线,棕色虚线箭头表示富聚合物相; (B) 浊点实验绘制的PVB-乙醇-甲苯三元相图;(C) 将甲苯滴加到 PVB 乙醇溶液中(溶液的浊度表明聚合物溶液的相分离)

    Figure  3.  (A) Schematic diagram of polymer-solvent-non-solvent ternary phase diagram: the green solid line indicates the separation line of the mixture, and the blue gradient color area indicates the "glassy" area, the orange line indicates the equilibrium line of the mixture separation, and the brown dashed arrow indicates the polymer-rich phase; (B) the PVB-ethanol-toluene ternary phase diagram drawn by the cloud point experiment; (C) Toluene was added by titration to the PVB ethanol solution (The turbidity of the solution indicates the phase separation of the polymer solution)

    图  4  PVB-混合溶剂滴定实验及SEM图像:(A)PVB-混合溶剂-H2O三元相图示意图; (B) 滴定前后照片对比; (C)和(D)分别为PVB胶团在劣溶剂和良溶剂中的SEM图像

    Figure  4.  Titration experiment of PVB-mixed solvent and SEM images: (A) Schematic diagram of PVB-mixed solvent-H2O ternary phase diagram; (B) comparison of photos before and after titration; (C) and (D) are the SEM images of PVB in poor solvent and good solvent,respectively

    图  5  不同湿度下,不同PVB溶液流延成膜研究:(A)VIPS成膜过程示意图; (B) PVB/甲苯-乙醇溶剂-水三元相图及其在不同湿度下的组分轨迹图; 其中,蓝色虚线代表极低相对湿度,粉色虚线代表中等相对湿度,橙色虚线代表高湿度下的成分轨迹; (C) 在较高相对湿度下形成的 PVB 膜的 SEM 图像;(D) 高相对湿度下形成的薄膜的孔壁厚度(hT)和孔隙率与溶剂比例的关系; (E) 在较低相对湿度下形成的 PVB 膜的 SEM 图像

    Figure  5.  Study on casting film formation of different PVB solutions under different humidity: (A) Schematic diagram of VIPS film formation process; (B) PVB/toluene-ethanol solvent/water ternary phase diagram and its component trajectory diagram under different humidity; Among them, the blue dotted line represents the extremely low relative humidity, the pink dotted line represents the medium relative humidity, and the orange dotted line represents the composition trajectory under high humidity; (C) SEM images of the PVB film formed under high relative humidity; (D) Relationship between the pore wall thickness and porosity of the membrane formed under higher humidity with the proportion of solvent; (E) SEM images of the PVB film formed under lower relative humidit

    图  6  相对温度(A)较高或(B)较低时;不同比例溶剂成膜的应力应变曲线; 在相对温度(C)较高或(D)较低条件下形成的薄膜的杨氏模量

    Figure  6.  Under (A) high humidity and (B) low humidity film forming conditions, the stress and strain curves of different proportions of solvent film formation; Young's modulus of the film formed under (C) high humidity and (D) low humidity conditions.

    表  1  各基团的摩尔引力常数与摩尔体积

    Table  1.   Molar gravitational constant and molar volume of each group

    GroupGravitational constant /(${\rm{cal}}^{\frac {1}{2}}\cdot{\rm{cm}}^{\frac {3}{2}} $·mol−1)Molar volume/(cm3·mol−1)
    ―CH3148.333.5
    ―CH2131.516.1
    >CH―86.0−1.0
    ―O―(Ether,Acetal)115.03.8
    ―OH225.810.0
    下载: 导出CSV

    表  2  不同体积比的溶剂的溶度参数

    Table  2.   Solubility parameters of solutions in different volume fractions

    V
    (Toluene):V(EtOH)
    $ \delta $/(${ {\rm{cal} } }^\frac{1}{2}/{\rm{c}}{{\rm{m}}^{ - \frac{3}{2}}}$)ω1/(${ {\rm{cal} } }^\frac{1}{2}/{\rm{c}}{{\rm{m}}^{ - \frac{3}{2}}}$)Ω1/(cm3·mol−1
    4:110.062.359.78
    1:111.344.1510.54
    1:412.245.6710.84
    1:912.476.1310.86
    下载: 导出CSV
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  • 收稿日期:  2021-09-06
  • 录用日期:  2021-11-01
  • 网络出版日期:  2021-12-30

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